CN1311031C - Ionomer/polyamide blends with improved flow and impact properties - Google Patents

Ionomer/polyamide blends with improved flow and impact properties Download PDF

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CN1311031C
CN1311031C CNB038027305A CN03802730A CN1311031C CN 1311031 C CN1311031 C CN 1311031C CN B038027305 A CNB038027305 A CN B038027305A CN 03802730 A CN03802730 A CN 03802730A CN 1311031 C CN1311031 C CN 1311031C
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ionomer
acid
low
maleic anhydride
weight
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CN1622979A (en
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S·C·范伯格
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Dow Chemical Co
Dow Global Technologies LLC
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

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Abstract

An ionomer/polyamide blend with improved flow (e.g., lower viscosity) can be achieved while simultaneously maintaining or improving physical properties such as low temperature Izod impact resistance by the addition of low molecular weight ethylene/acrylic acid copolymer (e.g., so-called acid wax polymer derived from copolymerizing at least 5 weight percent and preferably greater than 9 weight percent acrylic acid and/or methacrylic acid with ethylene and having a melt index, ASTM D1238, preferably greater than 900 dg/min and most preferably greater than 5,000 dg/min). Optionally, the blends can further contain additives such as very low density polyethylene (VLDPE), ethylene propylene elastomer (EPR), ethylene propylene diene monomer elastomer (EPDM), corresponding maleic anhydride grafted elastomers (MAN-g-VLDPE; MAN-g-EPR; and MAN-g-EPDM), or mixtures thereof. The blends exhibiting improved flow characteristics according to the invention are particularly useful in the manufacture of automotive parts, panels and the like having a class A surface.

Description

Ionomer/polyamide blend with improved flowability and impact property
Technical field
The present invention relates to have the ionomer/polyamide blend of improved flowability and impact property, with and preparation method thereof.More particularly, but be not as limitation of the present invention, the present invention relates in ionomer/polyamide blend, add the ethylene, propylene elastomerics (MAN-g-EPR) of low-molecular-weight ethylenic/vinylformic acid (methacrylic acid) multipolymer, very low density polyethylene (VLDPE), ethylene, propylene elastomerics (EPR), maleic anhydride graft, very low density polyethylene (MAN-g-VLDPE) or its mixture of maleic anhydride graft, thereby when reducing blend viscosity, keep or improve the low temperature arm-type impact property of hanging oneself from a beam.
Background technology
This area is known usually: will be used for based on the thermoplasticity fusion plastics of the blend of ionomer and high density polyethylene(HDPE) or polymeric amide with the outside automobile colored molded instrument panel of injection molding manufactured, bumper cover, side form product and other decoratiove finish.The concurrent mixture of this base polymer is disclosed in United States Patent (USP) 5,866, in 658, and can be available from E.I.du Pont de Nemoursand Company, trade mark is called Bexloy It comprises alpha-olefin, is generally ethene, and with α, β-vinyl unsaturated carboxylic acid is generally the multipolymer of vinylformic acid, methacrylic acid or its mixture, and wherein the acid group of the 65-100% of preferred acid multipolymer is with metal ion such as neutralizations such as zinc, sodium.These ionomers can be available from E.I.du Pont de Nemours and Company, and trade mark is called Surlyn In 1658 patents, height neutral acid copolymer preferably with one or more semicrystalline polyamides, for example policapram (nylon 6) and polyhexamethylene adipamide (nylon 66) blend.The difficulty of this blend is do not sacrificing its physical property, as realizing and keep best rheology under the prerequisite of shock resistance and tensile strength.
Summary of the invention
Consider the problems referred to above, have now found that to its adding or mix ethene and the low-molecular weight copolymer of vinylformic acid, methacrylic acid and its mixture, and optional one or more additives that add, for example EPDM and its mixture of the VLDPE of very low density polyethylene (VLDPE), maleic anhydride graft, ethylene propylene diene monomer (EPDM) rubber, maleic anhydride graft can improve the flowability of gained ionomer/polyamide blend when significantly not reducing physical property such as shock resistance, tensile strength.
Therefore the invention provides a kind of ionomer/polyamide blend, comprise for the ionomer/polyamide blend of per 100 weight parts with improved flow characteristics:
(i) ethene of 1-20 weight part and at least a low-molecular weight copolymer that is selected from other comonomer of vinylformic acid, methacrylic acid and its mixture, wherein low-molecular weight copolymer has the melting index (ASTM D1238) greater than 350dg/min, and the content of vinylformic acid and the mixed comonomer of methacrylic acid is at least 5%; With optional
(ii) one or more additives of 20 weight parts at the most, it is selected from VLDPE, ethylene, propylene (EPR) elastomerics, ethylene propylene diene monomer (EPDM) rubber, the EPR of maleic anhydride graft, EPDM of maleic anhydride graft and composition thereof of very low density polyethylene (VLDPE), maleic anhydride graft.
The present invention further provides a kind ofly when significantly not reducing shock resistance and tensile strength, reduced the ionomer/polyamide blend method of viscosity, comprised mixing step,, mixed for the ionomer/polyamide compound of per 100 weight parts
(i) ethene of 1-20 weight part and at least a low-molecular weight copolymer that is selected from other comonomer of vinylformic acid, methacrylic acid and its mixture, wherein low-molecular weight copolymer has the melting index (ASTM D1238) greater than 350dg/min, and the content of vinylformic acid and the mixed comonomer of methacrylic acid is at least 5%; With optional
(ii) one or more additives of 20 weight parts at the most, it is selected from VLDPE, ethylene, propylene (EPR) elastomerics, ethylene propylene diene monomer (EPDM) rubber, the EPR of maleic anhydride graft, EPDM of maleic anhydride graft and composition thereof of very low density polyethylene (VLDPE), maleic anhydride graft.
Low-molecular-weight multipolymer has and is low to moderate 350 melting index, but preferred molten index minimum is 900dg/min and at least 5%, preferred 9% weight or more vinylformic acid and the mixed co-monomer content of methacrylic acid.
Embodiments of the present invention
Unless stated otherwise, for the present invention, term " multipolymer " is meant two or more polymkeric substance that obtain as the different monomers polymerization of the reactant of replacing mutually in the polymerization process.Thereby term means and comprises " terpolymer " and by the polymkeric substance that produces more than three kinds of comonomers, also comprise " copolymer ".But when this term in order to expression during polymeric amide, its purpose is not meant and comprises the polymeric amide that is for example produced by independent dicarboxylic acid and a kind of diamines.Simultaneously term " substantially by ... form " to refer to the component of enumerating be necessary, and more a spot of other component also can exist not decrease in the amount of operability of the present invention.On the contrary, as long as interests of the present invention and/or advantage can also realize (for example, improved flowing and flow characteristics etc.), term " comprises " meaning and can have other relatively large component.
Useful ionomer/polyamide blend according to the present invention comprises that widely beta-unsaturated carboxylic acid multipolymer (being called acid copolymer at this) makes up or mix any thermoplasticity blending plastics of gained with polyamide thermoplastic based on neutralizing or part neutral ethylene/alpha.This blend can and strengthen with various fibers and other reinforcing filler usually.Particularly, the present invention relates to ionomer/polyamide blend, it is for being scattered in semicrystalline polyamides, the α of ethene in the nylon-6 and high weight percentage for example, the unsaturated C of β-vinyl 3-C 8The height neutral multipolymer of carboxylic acid.These blends are particularly useful for for example comprehensively having in the application of toughness, high gloss, friction resistant/scratch (damage), uvioresistant, hot properties and inflexible moulded piece of expection.Especially preferred ionomer/polyamide blend type for example is disclosed in U.S. Patent number 5,866, in 658.Prompting according to this reference, preferably include 60-40 (more preferably 50-45 in the blend, also preferred 60-55) % weight ionomer and 40-60 (more preferably 50-55, also preferred 40-45) % weight polyamide (per-cent is based on the gross weight of ionomer and polymeric amide), wherein polymeric amide forms successive (or altogether continuously) phase.Ionomer preferably exists with the percent by volume higher than polymeric amide, its be scattered in continuous or altogether the successive polymeric amide mutually in.In the accompanying drawing of 1658 patents as can be seen, ionomer has about 0.1 spherical particle basically to about 0.2 μ m mean diameter with trickle, major part, or the rectangle with average cross section diameter (minor axis length) of about 0.1 to about 0.2 μ m and curve or oval particulate homogeneous form be dispersed in continuous polymeric amide mutually in.
For polymeric amide and ionomer, can also contain in the blend just like ultraviolet ray (UV) photostabilizer, oxidation inhibitor, thermo-stabilizer, pigment and dyestuff, filler, slipproofing agent, softening agent, nucleator, other processing aid etc.For the ionomer/polyamide blend of per 100 weight parts, these components preferably exist with about 1 amount to about 3 (preferred about 1.5 to about 3) part, but also can exist with lower or higher levels of amount.
Be applicable to the α of ionomer of the present invention, the unsaturated C of β-vinyl by ethene and high weight percentage 3-C 8Carboxylic acid, the multipolymer of preferable methyl acrylic or methacrylic acid forms.Think that sour percentage composition " height " depends on the acid of use.In the situation of methacrylic acid, based on the gross weight of multipolymer, preferred 15-25% weight.For vinylformic acid, because the 14% preferably lower weight of difference of molecular weight.In final blend, the acid moieties metallic cation in the multipolymer, especially compatible positively charged ion, preferred zinc height neutralization (preferred 65-100%) with polymeric amide.
Ionomer of the present invention derives from ethene and usually with metal ion neutral α, the unsaturated C of β-vinyl 3-C 8The direct copolymer of carboxylic acid (" ethylene acid copolymer ").Be different from and monomer connected or be aggregated in " graft copolymer " on the existing polymer chain, " direct copolymer " refers to polymkeric substance is by the monomer polymkeric substance that obtains of polymerization mutually simultaneously.It is known preparing these ionomeric methods, and is disclosed in United States Patent (USP) 3,264, in 272.Ionomer based on the preparation of ethene-sour direct copolymer be disclosed in United States Patent (USP) 4,351, in 931.Because being separated of monomer-polymkeric substance is difficult to prepare the ethene-acid copolymer with higher level acid in the successive polymerization device.Yet pass through to use in the United States Patent (USP) 5028674 disclosed " solubility promoter technology ", or can avoid these difficulties by using than the high a little pressure of pressure of preparation lower acid multipolymer.
Ethene-the acid copolymer that is used to prepare ionomeric copolymers of the present invention can be an e/x/y copolymer, and wherein E is an ethene; X is the comonomer of the property of softening, and Y is α, the unsaturated C of β-vinyl 3-C 8Carboxylic acid, especially acrylic or methacrylic acid.Yet optimal ethylene-acid copolymer is dipolymer (comonomer of the non-property of softening).Preferred acid moieties is methacrylic acid and vinylformic acid.
" property of softening " refers to and makes polymkeric substance have relatively poor crystallinity.Suitable " property of softening " comonomer (X) is for being selected from the monomer of alkyl acrylate and alkyl methacrylate, wherein alkyl has 1-12 carbon atom, if it exists, can account for 30% weight (preferably at the most 25, most preferably at the most 15) of ethene-acid copolymer at the most.
It is preferred that ethene-sour dipolymer is ethylene/acrylic acid and ethylene/methacrylic acid.Other specific multipolymer comprises: the positive butyl ester/vinylformic acid of ethylene/acrylic acid, positive butyl ester/the methacrylic acid of ethylene/acrylic acid, ethylene/acrylic acid isobutyl ester/methacrylic acid, ethylene/acrylic acid isobutyl ester/vinylformic acid, positive butyl ester/the methacrylic acid of ethylene/methacrylic acid, ethylene/methacrylic acid methyl esters/vinylformic acid, ethylene/methyl acrylate/vinylformic acid, ethylene/methyl acrylate/methacrylic acid, positive butyl ester/the vinylformic acid of ethylene/methacrylic acid methyl esters/methacrylic acid and ethylene/methacrylic acid.
Has the acid moieties that exists with higher amount in order to the ionomeric ethene-acid copolymer of preparation the present invention.Whether this amount is considered to " height " depends on employed acid moieties, especially the molecular weight of acid moieties.In the situation of ethylene/methacrylic acid, the level of preferred acid is the 15-25% weight (preferred 18-25, more preferably 19-22) of multipolymer.For the situation of ethylene/acrylic acid, the level of preferred acid is the 14-25% weight (preferred 16-25, more preferably 18-22) of multipolymer.Particularly consider disclosed hereinly, for reaching predetermined glossiness and wear resistance, can determine that for other acid moieties those skilled in the art that need " height " sour water is flat.
Will be appreciated that the multipolymer that can mix more than one, wherein any or multiple sour water is put down outside " height " of the present invention scope, with the average acid level within the flat scope of sour water that obtains before the neutralization at preferred high percentage ratio.For the situation of mixture, preferably the weight percentage of acid should be near this preferable range, most preferably within this scope in each acid copolymer (ionomer component therefrom produces).
Acid moieties is preferably by metallic cation, and especially unit price and/or divalent metal height neutralize.Preferably use the metallic cation compatible neutralization with nylon, that is to say use also can with the interactional positively charged ion of the amido linkage of polymeric amide.Preferred metallic cation comprises lithium, magnesium, calcium and zinc, or these cationic combinations.Zinc most preferably.Less selection potassium and sodium.Potassium neutral ethylene acid copolymer is easy to absorb the moisture that nylon is had a negative impact.The sodium ionomer is difficult to stable existence under ultraviolet radiation.Magnesium and calcium preferably are used in combination with zinc.
Though it is neutralizing agent (for example magnesium oxide, zinc oxide and calcium oxide) can add with solid-state form, preferred as the adding of the enriched material in ethene-acid copolymer carrier.The preparation of enriched material can be by careful selected ethene-acid copolymer and mixing condition, to carry out with carrier in the not obvious ground of assurance neutralizing agent.Can also contain the salt (for example acetate and stearate) of one or more metallic cations of (up to about 2% weight) on a small quantity in this and in the enriched material.
For the form that reaches expection (ionomer be dispersed in continuous or altogether successive nylon mutually in), the ionomer higher level that neutralizes is made the viscosity of its viscosity greater than nylon.Preferably at first the more low viscous ethene-acid copolymer of part neutral is sneaked in the nylon, under violent blended condition, when melting mixing, further neutralize then to improve ionomeric viscosity.
Based on enlightenment herein, those skilled in the art will know: preferred neutralization levels will depend on the ethene-acid copolymer of use and the character of expection.Can regulate the gentle neutral degree of sour water to reach the special properties of expection.Improve the average acid level and can increase glossiness.Highly neutralization then produces the product harder, that glossiness is better, yet more appropriate neutralization produces more tough product.
Basically any polymeric amide can be used for mixture of the present invention, and benefits from the existence of flow improver additives.According to patent 1658, preferably semicrystalline polyamides is used for the present invention in addition.Term " semicrystalline polyamides " is conventionally known to one of skill in the art.Be applicable to semicrystalline polyamides of the present invention usually by lactan or amino acid preparation, or by the condensation prepared by diamine such as hexanediamine and diprotic acid such as sebacic acid.The multipolymer and the terpolymer that also comprise these polymeric amide.Preferred semicrystalline polyamides is polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6,6), and most preferably nylon 6.Other can be used for semicrystalline polyamides of the present invention and comprises Ni Long11, nylon 12, nylon 12,12, and multipolymer and terpolymer, for example nylon 6/6,6, nylon 6/6,10, nylon 6/12, nylon 6,6/12, nylon 6/6,6/6,10 and nylon-6/6T.
For the second-order transition temperature (Tg) that improves the nylon phase, can use amorphous polyamides instead of part semicrystalline polyamides.Polymeric amide mutually in about at the most 10% weight, preferably about at the most 5% weight can be amorphous polyamides.Term " amorphous polyamides " is known for a person skilled in the art." amorphous polyamides " of Shi Yonging is meant and lacks crystalline polymeric amide herein, shown in differential scanning calorimeter (" DSC ") is measured, lacks heat absorption crystallization melting peak (ASTM D3417) under 10 ℃/minute heating rate.
Between the example of operable amorphous polyamides comprises/paraphenylene terephthalamide's amine moiety ratio is isophthaloyl amine hexanediamine, the isophthaloyl amine hexanediamine/terephthalamide terpolymer, 2 of 100/0-60/40,2,4-and 2,4, mixture, hexanediamine and the 2 methyl pentamethylenediamine of 4-trimethylammonium hexanediamine terephthalamide and or the multipolymer of mixture of terephthalic acid or acid.Also can use based between contained high levels terephthalic acid part/polymeric amide of terephthalamide hexanediamine, condition is to mix first kind of diamines such as 2-methyl diamino pentane to produce a kind of machinable amorphous polymer.Amorphous polyamides can contain a small amount of lactams, and for example hexanolactam or ω lauryl lactan are as comonomer, even be not unbodied based on these polymer of monomers only, as long as they do not give crystallinity to polymeric amide.In addition, in the indefiniteness polymeric amide, can contain the liquid or solid softening agent of about at the most 10% weight, for example glycerine, Sorbitol Powder, mannitol or aromatic sulfonamide compound.
Amorphous polyamides can be the blend of ethylene-vinyl alcohol and amorphous nylon, wherein polyamide component comprise whole compositions of accounting for EVOH and polymeric amide about 5 to about 95% weight, preferred about 15 to about 70% weight, most preferably from about 15 to about 30% weight.
Should the preferred polyamide component under the melting mixing condition, have the sufficiently high viscosity that mechanical property can be provided, but it is also enough low to form the facies relationship of the ionomer/polyamide blend of expecting.The viscosity of polymeric amide should be than ethene-acid copolymer or ionomeric viscosity height under low neutral level, but should be lower than ionomeric viscosity under high neutral level.
As United States Patent (USP) 5,118,746 is disclosed, and the low-molecular-weight ethylenic/acrylic copolymer that joins the polymeric additive that is used as viscosity modified in ionomer/polyamide compound is the ethene and the multipolymer that is selected from the unsaturated carboxylic acid of vinylformic acid (E/AA multipolymer) and methacrylic acid (E/MAA multipolymer) with high fusion index (MI).Measure according to ASTM 1238 condition E, the multipolymer of viscosity modification has at least 350 and be preferably greater than the melting index of 900dg/min, more preferably be at least about 5,000dg/min, most preferably be at least about 10,000dg/min.The multipolymer of viscosity modified also preferably contains altogether at least about 5% weight, the carboxylic acid monomer of preferred at least 9% weight.Simultaneously, what preferred selection was used is ethylene/acrylic acid copolymer, makes it have identical carboxyl acid copolymer monomer content with the ionomer that uses.As long as keep suitable MI level, can have a spot of the 3rd comonomer.The 3rd comonomer can be to be selected from C 3-C 7α, the C of beta-unsaturated carboxylic acid 1-C 10The copolymerisable monomer of alkyl ester, vinyl ester, vinyl ether, vinyl cyanide, methacrylonitrile, carbon monoxide and sulfurous gas.
Usually select the relative quantity of the multipolymer of the viscosity modified of using according to the MI that wishes to get.On the mathematics, when using about at the most 20% weight E/AA or E/MAA, the linear direct ratio of weight percentage of the logarithm of the MI of the ionomer/polyamide blend of gained viscosity modification and the ethylene/acrylic acid copolymer of use.Yet should be known in that for the purposes of the present invention at the polymkeric substance loading level that improves viscosity during greater than 20% weight, effect of the present invention can partly realize, and should consider a suitable amount for the present invention.Even under high filler loading capacity more, the physical properties of gained mixture also may begin to reduce.
The viscosity modified copolymer of aforesaid high fusion index can be available from HoneywellPerformance Polymers and Chemicals, and trade mark is called AC Multipolymer (E/AA multipolymer).These multipolymers also can be according to United States Patent (USP) 3,264, and one section of 272 openly is prepared.
Be mixed with to choose wantonly in the ionomer/polyamide blend of multipolymer of modification viscosity and contain one or more other additives, for example very low density polyethylene (MAN-g-VLDPE) or its mixture of the ethylene propylene diene monomer elastomer/rubber (MAN-g-EPDM) of the ethylene, propylene elastomer/rubber (MAN-g-EPR) of very low density polyethylene (VLDPE), ethylene, propylene elastomer/rubber (EPR), maleic anhydride graft, ethylene propylene diene monomer elastomer/rubber (EPDM), maleic anhydride graft, maleic anhydride graft.Being used for very low density polyethylene of the present invention (VLDPE) is any linear polyethylene known in the art basically, has about 0.89 to about 0.915 density.This very low density polyethylene is general main to be by ethene and at least a C 3-C 8The co-polymerization production of alpha-olefin comonomer.The very low density polyethylene of maleic anhydride graft (MAN-g-VLDPE) is the VLDPE of the maleic anhydride graft of several weight percentage.Generally based on the weight of VLDPE, the maleic anhydride of 1-2% is enough.Being used for ethylene, propylene elastomerics of the present invention (EPR) in fact also is this area known those elastomericss usually.Preferred EPR is the EPDM elastomeric terpolymer of ethene, propylene and the 3rd comonomer non-conjugated diene.These elastomericss are disclosed in United States Patent (USP) 3,658, in 752,3,758,643 and 4,078,020.MAN grafted EPR and/or EPDM are general also to be obtained by the graft reaction of the maleic anhydride of 1-2% weight.The graft reaction that is used for the reality of introducing maleic anhydride on additive can carry out with the common known method of prior art basically.For the purposes of the present invention, very relevant with similar acid anhydride structure or may be as other unsaturated dicarboxylic acid of the precursor of similar acid anhydrides behind graft reaction, for example fumaric acid, methylene-succinic acid, methylfumaric acid be considered to be equal to the MAN in the MAN grafting additive.Can use optional additive, it accounts for about 20% weight of amount of the mixture at the most.Yet should be known in that for the purposes of the present invention at the loading level of the polymkeric substance that improves viscosity during greater than 20% weight, effect of the present invention can partly realize, thereby should consider a suitable amount for the present invention.Even more under the high filler loading capacity, the physical properties of gained mixture also may begin to reduce at these.
The mixture of viscosity modified in fact of the present invention can advantageously contain more a spot of, general to other additive that reaches several percentage ratios, for example pigment, tinting material, carbon black, ultraviolet ray (UV) stablizer, oxidation inhibitor, processing aid, glass fibre, mineral filler, slipproofing agent, softening agent, nucleator etc.Above-mentioned various additive and separately purposes be well known in the art, and commercial in conjunction with ionomer/polyamide blend should be used for use.General preferably combination is used, and understands typical preferably combination in an embodiment specifically.
The preparation of blend of the present invention can be undertaken by using standard hybrid mode well known in the art.The preferred industrial mixers of using, kneader for example, or commercial thermoplastic extrusion machine, especially twin-screw extruder wait the mixing fully that reaches component, and reach the homodisperse of component.Perhaps last homodisperse can be produced in the final injection-moulding plastic process of object and finish being combined as starting material with independent component, intermediate, component precursor or its.Selectivity and availability according to starting ingredient also can mix stage by stage.Thereby, commercially available ionomer/polyamide blend can with ethylene/acrylic acid copolymer FLOW IMPROVERS and other additive for example the ethylene, propylene elastomerics (MAN-g-EPR), ethylene propylene diene monomer elastomerics (EPDM), the ethylene propylene diene monomer elastomerics (MAN-g-EPDM) of maleic anhydride graft, the very low density polyethylene (MAN-g-VLDPE) or the direct co-extrusion of its mixture of maleic anhydride graft of very low density polyethylene (VLDPE), ethylene, propylene elastomerics (EPR), maleic anhydride graft.Perhaps can be simultaneously with ionomer, polymeric amide and ethylene/acrylic acid copolymer and other optional additive co-extrusion mixing to obtain expecting.By adding metal hydroxides, metal oxide etc., can further on purpose improve ionomeric degree of neutralization at mix stages.In the co-extrusion stage, can further use the multipolymer of metal component neutralization of ethylene and copolymers of unsaturated carboxylic acids (that is ionomeric copolymer precursor), thereby at this ionomer of mix stages in-situ preparing.
Because highly neutralization, ionomeric viscosity will be above the polymeric amide under the processing conditions.Thereby preferred single step is handled or " original position neutralization " handled.If before mixed with molten polyamide, ethene-acid copolymer is partly neutralized to is lower than the level of final requirement, or preferred, if ionomer, for example various Surlyn Ionomer, especially have the peracid level, available from the ionomer of E.I.du Pontde Nemours and Company as initial ionomer, it mixes further to be neutralized to the degree of neutralization of prescribed percentage with polymeric amide simultaneously or subsequently, then handles and may be greatly simplified.As the explanation among the following embodiment, processing can advantageously be carried out by the classification extrusion machine with a plurality of opening for feeds, wherein part neutral ionomer, polymeric amide, ethylene/acrylic acid copolymer flow ability modifying agent and other additive, for example the very low density polyethylene (MAN-g-VLDPE) of the ethylene propylene diene monomer elastomerics (MAN-g-EPDM) of very low density polyethylene (VLDPE), ethylene propylene diene monomer elastomerics (EPDM), maleic anhydride graft, maleic anhydride graft can on purpose be added to the single different zones of extruding mixing equipment.
In order to meet the requirements of form, with preferably use cationic moiety neutral ethene-acid copolymer compatible and polymeric amide with nylon should be under well-mixed condition (high-shear) melting mixing, and further neutralize mixing when taking place.Mixed should under the intensity that is enough to obtain desired form, temperature and residence time, carrying out.The system that needs effective devolatilization is to remove the water that forms in the N-process.If start from less neutralization or do not have in and the time owing to generated more water, then the efficient of devolatilization is more important.In melt compounding, preferably should there be at least one at least 630 to be the vacuum band of mmHg, to remove moisture.
Can at first various starting ingredient be mixed with the form that is commonly referred to " salt green pepper shape " mixture.They can be mixed by simultaneous or the meter that separates, perhaps they separately and by one or more inlets can be entered mixing equipment, for example the one or more mixed section of extrusion machine, Banbury mixer, Buss malaxator, Farrell continuous mixers etc.If can use more than one extrusion machine feed zone, nylon, preferably can add at last opening for feed as the neutralizing agent of enriched material and part ionomer, ionomeric rest part adds at feed zone subsequently.The polymkeric substance slice that leaves from extrusion machine preferably quenched in water-bath before being cut into little.Can use well known in the art other to be used for process for granulating and comprise cutting and air quenching under water.
The embodiment that below provides is in order to full-time instruction the present invention, and further illustrates all respects of the present invention and characteristics.Thereby these statements are used for illustrating difference of the present invention and advantage, rather than are used for excessively restriction.Unless otherwise noted, be mixed among each embodiment in five heating zone, 28 millimeters twin-screw extruders and carry out, the static mixer of Kenics company is housed between the top of this extrusion machine and single casement dish.In all cases, this extrusion machine is at screw speed, the vacuum porthole (port) of 200 rotating speeds/minute (rpm) that 630 millimeters mercury are leant on, the component feeding rate of each feed zone of extrusion machine is to operate under the about 10 Pounds Per Hours condition.The nitrogen isolation layer is remained on the hopper.Temperature distribution along the pipeline section of extrusion machine is: trunnion: about 25 ℃; Section 1:220 ℃; Section 2,3,4 and 5:250 ℃; Joint 1 and 2:250 ℃; Mould: 265 ℃.The residence time of sample is about 2.5 minutes.Before cutting into pieces, sample quenches in water-bath (about 23 ℃).
Use molded test rod (5 inches * 1/2 inch * 1/8 inch), plate (3 inches * 5 inches * 1/8 inch) and the dish (3 inches * 1/8 inch) that is used for physical test of single screw rod injection moulding machine.Unless otherwise noted, in all cases the sample injection molding is being used in the injection molding machine of Universal screw rod at 6 ounces of capacity, setting roller temperature to reach the melt temperature in 260 ℃ scope.The molded condition of using is the spiro rod rate of quick punching press rate of advance, 60rpm, the back pressure of 50 pounds per square foots (gauge pressure), the injection pressure of 400-800 gauge pressure, 20 seconds injection length, 30 seconds residence time and 5/32 inch nozzle.
Use different test conditions to determine physical property.According to ASTM D1238, condition E determines melting index (MI) under 190 ℃ of temperature and 2160 gram heavy burdens.Use the kapillary of 30 millimeters of length, 1 millimeter of diameter to measure melt viscosities at 240 ℃.According to ASTM D1708, determine tensile strength with plate (3 inches * 5 inches * 1/8 inch) cross cutting rod (1 1/2 inches * 5/8 inch * 1/8 inch).Be to test on the instron (Instron) of 2 inch per minute clocks in crossbeam speed.Modulus in flexure is according to ASTM D790, and (5 inches * 1/2 inch * 1/8 inch) proof stick by 2 inches of spans carries out.Recess is hung oneself from a beam arm-type shock strength according to ASTM D256, uses and be processed with 0.1 inch recess on the face of rod
Figure C0380273000131
Rod carries out.Rod is cut in half by one 5 inches * 1/2 inch * 1/8 inch moulded rod and obtains (that is one near the cast gate section, another is a far-end).
Starting material, its feature and commercial source separately are summarized as follows:
The AC540-95/5:E/AA copolymer waxes, acid number (mg KOH/gm)=40, density=0.93gm/cc, MI＞15,000, Mettler dropping point=105 ℃ (Honeywell).
The AC5120-85/15:E/AA copolymer waxes, acid number (mg KOH/gm)=120, density=0.94gm/cc, MI＞15,000, Mettler dropping point=92 ℃ (Honeywell).
Chimassorb 944FD-hindered amine as light stabilizer (Ciba-Geigy company).
Flexometer DFDU1085=ethylene/butylene VLDPE,＞15% butylene, density=0.884-0.900, MI=3-4 (Union Carbide company)
The HPU=E/MAA multipolymer; 19.0%MAA, 1714M.I.
Irganox 1010=tetramethylene (3,5-di-t-butyl-4-hydroxyl cortex cinnamomi acid ester) (Ciba-Geigy company).
Irganox B1171=1: 2 Irganox 1010 and Irgafos 168 blends, Irgafos 168=three (2, the 4-di-tert-butyl) phosphoric acid ester (Ciba-Geigy company).
Nordel The 2722=narrow molecular weight distribution elastomer, 72/21/7: ethylene/propylene/hexadiene terpolymer (DuPont)
Surlyn The 9120-81/19:E/MAA multipolymer, with in the zinc and 36%, base resin MI=60; Ionomer MI=1.0
Tinuvin 779DF=UV stablizer (Ciba-Geigy company)
The Nordel of TRX-101-maleic anhydride graft 2744; Nominal 2.1%MAN; MI=1.5～5
Ultramid =nylon 6; RV=2.8 (BASF)
Embodiment 1
According to the method for above-mentioned general introduction, prepared a series of polymeric amide and ionomeric 7 batches of different mixture things, and tested.In every batch of blend, blend comprise based on 81% weight ethene and 19% weight methacrylic acid copolymerization and multipolymer ionomer and based on the polymeric amide (Ultramid of nylon 6 B3), wherein in the ionomer carboxyl be generally 68-71% (Surlyn by zinc neutral degree of neutralization 9120, MI=1.1).In the seven batches of blends six batches comprise a kind of as flowing additive in two kinds of different low-molecular-weight ethylenic multipolymers, promptly with the ethene of vinylformic acid (AC5120) copolymerization of the vinylformic acid (AC540) of 5% weight or 15% weight.Wherein two batches of blends also contain EPDM rubber (TRX-101) additive of maleic anhydride graft except containing the ethylene copolymer flowing additive.A collection of blend contains extra additive EPDM rubber (Nordel 2722), a kind of extra additive VLDPE (Flexomer DFDU1085) that contains.Control group is a kind of corresponding polyamide/ionomer blend that does not have additive.The details of composition and gained data are listed in the table 1.In each case, by adding the fusion that ethylene/acrylic acid copolymer increases blend.As shown in Table, compare with control group, the ethylene/acrylic acid copolymer flow ability modifying agent does not damage the low temperature cantilever-type impact strength significantly.
Table 1
RUN 1 2 3 4 5 6 7
ULTRAMIDB3 40.4％ 38.2％ 38.2％ 38.2％ 36.0％ 36.0％ 36.0％
SURLYN9120 46.5％ 44.0％ 44.0％ 44.0％ 41.5％ 41.5％ 41.5％
AC540(5％AA) - 5.0％ - - - - -
AC5120(15％AA) - - 5.0％ 2.5％ 5.0％ 5.0％ 5.0％
TRX-101 - - - 2.5％ - - -
NORDEL2722 - - - - 5.0％ 5.0％ -
Flexometer DFDU1085 - - - - - - 5.0％
ZnO enriched material (CS8749-5) 5.6％ 5.3％ 5.3％ 5.3％ 5.0％ 5.0％ 5.0％
Sodium hypophosphite 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％
Reed is deceived CNY61696 3.9％ 3.8％ 3.8％ 3.8％ 3.8％ 3.8％ 3.8％
Tensile property during room temperature
Surrender tension force (psi) 5,150 4,810 4,970 4,750 4,580 3,890 3,950
Elongation at yield (%) 20％ 21％ 23％ 21％ 21％ 7％ 7％
Maximum tension (psi) 7,410 4,830 6,560 6,210 6,210 4,370 4,260
Maximum tension elongation (%) 250％ 76±75％ 230％ 220％ 240％ 36％ 34％
Breaking tension (psi) 7,410 4,480 6,560 6,210 6,210 N/D N/D
Extension at break (psi) 250％ 150％ 230％ 220％ 240％ 120％ 140％
Modulus in flexure 140,100 136,300 141,600 138,800 123,600 118,400 123,300
Recess cantilever-type impact strength in the time of-30 ℃
Gate end 3.62 2.82 5.10 6.19 5.60 4.76 5.65
Far-end 4.62 3.75 5.27 6.17 5.52 5.03 5.33
Embodiment 2
In order to further specify flow modifier blend enhanced flow characteristics of the present invention, and the method for preparing these blends, prepare other 10 batches and contained polymeric amide (Ultramid B3) and ionomer (Surlyn 9120) blend, and it is tested.Use feed extruder along separate routes, with Surlyn 9120 adverse current feedings are with the polymeric amide forward feeding.(AC5120 is 15%AA) with three kinds of different concns (12,9 and 6% weight) and three kinds of positions (that is: all adverse current feedings, all forward feeding and not only adverse current feeding but also forward feeding) combined feed with flow modifier additives.The gained data are listed in the table 2.Can learn from data: when adding polymeric amide with adverse current adding ionomer and with adverse current, it is the most effective to the melt viscosity and the increase melt index that reduce blend to increase the AC resin concentration.Along with the increase of AC5120 concentration, the low temperature notched cantilever-type impact strength slightly reduces, yet the room temperature cantilever-type impact strength does not change basically.
Table 2
* Run 1 2 3 4 5 6 7 8 9 10
Adverse current feeding Surlyn9120 41.8％ 36.6％ 37.9％ 39.2％ 29.8％ 32.8％ 35.8％ 29.8％ 32.8％ 35.8％
AC5120(15％AA) - - - - 6.0％ 4.5％ 3.0％ 12.0％ 9.0％ 6.0％
ZnO enriched material (CS8749-5) 2.3％ 2.0％ 2.0％ 2.1％ 2.3％ 2.3％ 2.3％ 2.3％ 2.3％ 2.3％
Forward feeding ULTRAMIDB3 52.3％ 45.8％ 47.4％ 49.0％ 52.3％ 52.3％ 52.3％ 52.3％ 52.3％ 52.3％
AC5120(15％AA) - 12.0％ 9.0％ 6.0％ 6.0％ 4.5％ 3.0％ - - -
Zinic stearas 1.5％ 1.5％ 1.5％ 1.5％ 1.5％ 1.5％ 1.5％ 1.5％ 1.5％ 1.5％
Sodium hypophosphite 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％ 0.2％
Proximate nylon % volume 51.3％ 44.1％ 45.9％ 47.7％ 51.2％ 51.2％ 51.2％ 51.2％ 51.2％ 51.2％
Proximate SURLYN  % volume 48.7％ 42.0％ 43.6％ 45.3％ 34.7％ 38.2％ 41.7％ 34.7％ 38.2％ 41.7％
The volume % ratio of nylon/SURLYN  1.05 1.05 1.05 1.05 1.48 1.34 1.23 1.48 1.34 1.23
Phase inversion (J/g)
Rate of extrusion (lb/hr) 20.1 24.9 24.9 24.9 25.2 24.9 24.9 24.6 24.9 25.2
Ball sheet (J/gm) 24.8 - - - 18.8 23.7 21.9 - 20.6
Melt index (240 ℃/2.16kg) 2.2 6.0 4.6 2.6 6.9 4.9 4.0 3.4 5.6 5.4
30 ℃ of following recess cantilever-type impact strength-self colours
Gate end 4.36 1.74 1.92 2.06 2.03
Far-end 4.90 1.69 1.87 2.36 2.15
Recess cantilever-type impact strength under the room temperature-natural
Gate end 27.8 27.7 28.3 28.2 27.9
Far-end 27.3 25.4 25.6 26.2 25.8
Embodiment 3
With to embodiment 2 in similar mode, prepared other several with the shunt feed process and contained polymeric amide (Ultramid B3) and ionomer (Surlyn 9120) blend, and test.By add ethylene/acrylic acid copolymer (AC5120,15%AA) or sour co-monomer content ethylene/methacrylic acid (HPU E/MAA much at one; 19.0%MAA), come each blend of modification.The gained data are listed in the table 3.These data show: add ethylene/methacrylic acid or ethylene/acrylic acid copolymer in ionomer/polyamide blend, in the improvement of flowability E/MAA comparison E/AA is had good a little influence.
Table 3
Adverse current feeding Lot number 1 2 3 4 5 6
SURLYN 9120 41.80％ 32.79％ 32.79％ 33.95％ 33.95％ 29.88％
AC5120(15％AA) - 4.50％ - 3.00％ - -
HPU E/MAA - - 4.50％ - 3.00％ 6.38％
ZnO enriched material (CS8749-5) 2.25％ 2.25％ 2.25％ 2.25％ 2.25％ 2.39％
CHIMASSORB 944FD 0.94％ 0.94％ 0.94％ 0.94％ 0.94％ 1.00％
TINUVIN 234 0.47％ 0.47％ 0.47％ 0.47％ 0.47％ 0.50％
IRGANOX 1010 0.20％ 0.20％ 0.20％ 0.20％ 0.20％ 0.21％
IRGANOX B1171 0.37％ 0.37％ 0.37％ 0.37％ 0.37％ 0.39％
Forward feeding ULTRAMID B3 52.30％ 52.30％ 52.30％ 54.14％ 54.14％ 51.06％
AC5120(15％AA) - 4.50％ - 3.00％ - -
HPU E/MAA 123- A6：30 (19.0％MAA，1714 Ml) - - 4.50％ - 3.00％ 6.38％
Zinic stearas 1.50％ 1.50％ 1.50％ 1.50％ 1.50％ 1.60％
Sodium hypophosphite 0.170％ 0.180％ 0.180％ 0.180％ 0.180％ 0.19％
Modulus in flexure 114,700 117,400 126,100 118,200 122,500 120,600
Recess cantilever-type impact strength-self colour in the time of-30 ℃
Gate end 2.74 1.22 2.38 2.38 2.69 2.45
Far-end 3.16 2.03 3.31 3.03 3.23 2.20
Recess cantilever-type impact strength during room temperature-natural
Gate end 27.5 27.0 28.2 25.9 26.8 30.4
Far-end 29.4 26.3 28.7 27.7 28.8 28.0
Capillary rheology in the time of 240 ℃ is learned (shear viscosity, pascal * second) and (shear rate, second -1)
24.3 2,018.3 1,466.6 1,403.6 1,413.3 1,495.6 1,442.4
206.7 775.6 546.6 533.6 546.1 602.5 564.3
401.3 550.9 400.7 393.4 403.3 433.6 414.2
595.9 445.5 333.7 324.6 329.9 351.3 343.0
997.2 334.2 259.8 242.1 247.6 268.1 269.4
997.2 338.1 231.0 255.1 266.4 292.5 261.6
1471.5 271.3 187.7 206.0 212.6 232.3 212.6
Embodiment 4
With to front embodiment in similar mode, use the 30mm extrusion machine, 100rpm and flow rate greater than 251bs./hour condition under operation prepared other one group 6 batches by the shunt feed process and contained polymeric amide (Ultramid B3) and ionomer (Surlyn 9120) metal coloring blend, and test.In each blend, preparation 1-3 criticizes blend under three silver color colorants loading concentration that increase gradually, with the reduction of explanation shock strength when having splint in these blends.Lot number 4-6 relate to by add MAN-g-EPDM, each blend of modification with the ethylene/propylene/hexadiene terpolymer (TRX-301) of 2.1% maleic anhydride graft.The gained data are listed in the table 4.These data show: along with the painted increase of splint, cantilever-type impact strength reduces gradually 24 ℃ and 0 ℃.Lot number 3-6 explanation: by adding the MAN-g-EPDM rubber of 5% weight, the impact loss of energy returns to the value that has more non-pigmented ionomer/polyamide blend feature basically.
Table 4
Lot number 1 2 3 4 5 6
Explain Contain the contrast (after 1 hour) of silver color colorant Contain the contrast (after 2.5 hours) of silver color colorant Contain the contrast (after 5 hours) of silver color colorant 140-1 contains 5%TRX-301 140-2 contains 5%TRX-301 140-3 contains 5%TRX-301
Adverse current feeding Surlyn9120 41.39％ 40.78％ 39.81％ 29.31％ 38.68％ 37.69％
ZnO enriched material (CS8749-5) 2.23％ 2.20％ 2.14％ 2.12％ 2.09％ 20.40％
Forward feeding ULTRAMIDB3 51.78％ 51.02％ 49.80％ 49.15％ 48.41％ 47.20％
TRX-301 0 0 0 5.00％ 5.00％ 5.00％
Zinic stearas 1.49％ 1.46％ 1.43％ 1.41％ 1.39％ 1.36％
Sodium hypophosphite 0.17％ 0.17％ 0.17％ 0.16％ 0.16％ 0.16％
Silver color colorant 790-20-E 0.99％ 2.44％ 4.76％ 0.99％ 2.44％ 4.76％
Tensile property (under 150 ℃)
Surrender tension force (psi) elongation at yield (%) 760 11％ 870 12％ 870 13％ 830 12％ 840 12％ 830 12％
Breaking tension (psi) extension at break (psi) 1,860 318％ 2,250 320％ 2,030 312％ 1,860 308％ 1,900 318％ 2,010 317％
Elongation (%) during maximum tension (psi) maximum tension 2,160 310％ 2,290 315％ 2,200 306％ 2,030 300％ 2,060 302％ 2,080 309％
Recess cantilever-type impact strength-silver metal the look of (24 ℃) during room temperature
Gate end 23.3 19.9 17.5 23.4 23.2 20.2
Far-end 25.1 23.3 20.8 23.6 22.8 21.9
Recess cantilever-type impact strength-silver metal look in the time of 0 ℃
Gate end 9.67 6.83 5.18 18.0 10.9 8.35
Far-end 12.5 8.10 5.73 18.4 12.1 8.71
Recess cantilever-type impact strength-silver metal look in the time of 30 ℃
Gate end 3.59 2.86 3.00 3.11 2.76 2.73
Far-end 4.10 3.29 3.04 3.39 3.42 2.71
Capillary rheology is learned (shear viscosity, pascal * second)-black in the time of 240 ℃
Date 9/19/01 9/19/01 9/19/01 9/19/01 9/19/01 9/19/01
24.3 206.7 401.3 595.9 997.2 997.2 1,471.5 2,032.7 777.1 555.1 448.8 339.0 332.3 265.2 2,089.7 836.8 605.2 492.7 371.5 372.2 294.9 2,002.7 818.2 593.0 486.5 366.5 369.4 295.5 2,040.8 914.3 657.7 518.0 381.2 401.8 313.2 2,318.3 929.0 660.6 530.9 398.9 404.3 317.1 2,253.0 962.9 684.7 537.3 393.6 419.0 323.8
Industrial applicibility
As mentioned above, add in the ionomer/polyamide blend or mix the ethylene, propylene elastomer (MAN-g-EPR) of low-molecular-weight ethylenic/acrylic acid (methacrylic acid) copolymer, very low density polyethylene (VLDPE), ethylene, propylene (EPR) elastomer, maleic anhydride graft, very low density polyethylene (MAN-g-VLDPE) or its mixture of maleic anhydride graft, can reduce the viscosity of gained blend and keep simultaneously or improve the low temperature cantilever-type impact strength. Gained blend of the present invention demonstrates the viscosity of reduction and the flowability of improvement, especially can be used for making automobile component with A level surface, instrument board etc.

Claims (10)

1. blend with ionomer/polymeric amide of improved flowability, the ionomer/polyamide blend for per 100 weight parts comprises:
(i) ethene of 1-20 weight part and at least a low-molecular weight copolymer that is selected from other comonomer of vinylformic acid, methacrylic acid and composition thereof, wherein said low-molecular weight copolymer has the melt index of measuring according to ASTM D1238 greater than 350dg/min, and the content of vinylformic acid and the mixed comonomer of methacrylic acid is at least 5% weight; Randomly
(ii) one or more of 20 weight parts are selected from the additive of ethylene propylene rubber, the ethylene propylene diene monomer rubber of very low density polyethylene, ethylene propylene rubber, the maleic anhydride graft of very low density polyethylene, maleic anhydride graft, ethylene propylene diene monomer rubber of maleic anhydride graft and composition thereof at the most.
2. the ionomer/polyamide blend in the claim 1, the low-molecular weight copolymer of wherein said ethene and at least a other comonomer has the melt index of 900dg/min at least.
3. the ionomer/polyamide blend of claim 1, the content of the mixed comonomer of vinylformic acid and methacrylic acid is at least 9% weight in the low-molecular weight copolymer of wherein said ethene and at least a other comonomer.
4. one kind is not significantly reduced low-temperature impact resistance, and reduces the ionomer/polyamide blend method of viscosity, comprises the step of mixing following component, for the ionomer/polyamide blend of per 100 weight parts:
(i) ethene of 1-20 weight part and at least a low-molecular weight copolymer that is selected from other comonomer of vinylformic acid, methacrylic acid and composition thereof, wherein said low-molecular weight copolymer has the melt index of measuring according to ASTM D1238 greater than 350dg/min, and the content of vinylformic acid and the mixed comonomer of methacrylic acid is at least 5% weight; Randomly
(ii) one or more of 20 weight parts are selected from the additive of ethylene propylene rubber, the ethylene propylene diene monomer rubber of very low density polyethylene, ethylene propylene rubber, the maleic anhydride graft of very low density polyethylene, maleic anhydride graft, ethylene propylene diene monomer rubber of maleic anhydride graft and composition thereof at the most.
5. the method for claim 4, the low-molecular weight copolymer of wherein said ethene and at least a other comonomer has the melt index of 900dg/min at least.
6. the method for claim 4, the content of the mixed comonomer of vinylformic acid and methacrylic acid is at least 9% weight in the low-molecular weight copolymer of wherein said ethene and at least a other comonomer.
7. the metal ionomer/polyamide blend of a claim 1, comprising: be at most one or more described additives of 20 weight parts, wherein said blend has improved impact property.
8. the metal ionomer/polyamide blend in the claim 7, wherein said additive is the ethylene propylene diene monomer rubber of maleic anhydride graft.
9. a recovery is according to the method for the shock resistance of the metal ionomer/polyamide blend that claim 7 characterized, comprise ionomer/polyamide blend, be mixed to the step of one or more described additives that mostly are 20 weight parts for the metal coloring of per 100 weight parts.
10. the method in the claim 9, wherein said additive is the ethylene propylene diene monomer rubber of maleic anhydride graft.
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